WO1999054426A1 - Aqueous emulsion fuels from petroleum residuum-based fuel oils - Google Patents
Aqueous emulsion fuels from petroleum residuum-based fuel oils Download PDFInfo
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- WO1999054426A1 WO1999054426A1 PCT/US1999/008492 US9908492W WO9954426A1 WO 1999054426 A1 WO1999054426 A1 WO 1999054426A1 US 9908492 W US9908492 W US 9908492W WO 9954426 A1 WO9954426 A1 WO 9954426A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
Definitions
- This invention relates to liquid fuels known variously as bunker fuels and residual fuels, and to substitutes for these fuels that offer the advantages of lower viscosity and cleaner burning.
- Bunker fuels are heavy residual oils used as fuel by ships and industry, and in large- scale heating installations.
- the fuel oil known as No. 6 fuel oil which is also known as “Bunker C” fuel oil, is used in oil-fired power plants as the major fuel and is also used as a main propulsion fuel by deep draft vessels in the shipping industry.
- the fuel oils known as No. 4 and No. 5 fuel oils are used in commercial applications such as schools, apartment buildings, and other large buildings, and for large stationary and marine engines.
- the heaviest fuel oil is the vacuum residuum from the fractional distillation, commonly referred to as "vacuum resid," with a boiling point of 565°C and above. Vacuum resid is primarily used as asphalt and coker feed.
- the viscosity of the numbered fuel oils increases with the numerical designation.
- Fuel oil Nos. 4, 5, and 6 thus have higher viscosities and specific gravities than Nos. 1, 2 and 3, and vacuum resid has the highest. Because of their high viscosity, both vacuum resid and the higher numbered fuel oils generally require heating before they can be pumped. Of the numbered fuel oils, No. 6 fuel oil has the highest specific gravity (typically 0.9861 at 2
- residuum-based fuel oils such as vacuum resid, visbroken vacuum resid, liquefied coke, and fuel oil Nos. 4, 5, and 6 can be converted into low-viscosity, clean-burning liquid fuels by combining the oil with an aqueous liquid to form a macroemulsion, and incorporating sufficient emulsion stabilizer(s) to stabilize the emulsion.
- the resulting fuel emulsion is useful as a substitute for the non-emulsified fuel oil.
- the emulsion prepared from No. 6 fuel oil can be used in any furnace, boiler, engine, combustion turbine or power plant where No. 6 fuel oil has heretofore been known for use.
- the emulsion prepared from vacuum resid, visbroken vacuum resid, or liquefied coke can be used as a substitute for No. 6 fuel oil or lower-numbered fuel oils.
- the viscosity of the resulting emulsion is low enough to permit pumping of the emulsion at ambient temperature, which is particularly valuable for emulsions formed with No. 6 fuel oil.
- the burning of the emulsion offers significant reductions in NO x and particulates relative to the non-emulsified fuel oil. This reduces the need and cost of exhaust gas treatment. There is also a significant reduction in the amount of soot generated, which reduces maintenance and, in boilers, improves heat transfer efficiency.
- Emulsions prepared from vacuum resid or visbroken vacuum resid offer the further advantage of having the characteristics of the numbered fuel oils without requiring blending of the resid with a cutter stock (i.e., a distillate fraction). This provides a cheaper alternative to the numbered fuel oils.
- FIG. 1 is a plot of NO x reduction by rebuming in a boiler as a function of the proportion of heat input supplied by the rebuming stage, for three different rebuming fuels, one of which is within the scope of this invention.
- the NO x concentration prior to the rebuming stage was 450 ppm.
- FIG. 2 is a plot similar to that of FIG. 1 except that the NO x concentration prior to the rebuming stage was 800 ppm.
- FIG. 3 is a plot of NO x reduction in a rebuming stage as a function of stoichiometric
- FIG. 4 is a plot of NO x reduction in a rebuming stage as a function of the proportion of heat input supplied by the rebuming stage, for two different macroemulsions within the scope of this invention, at two different NO x concentrations prior to the rebuming stage.
- FIG. 5 is a plot of NO x reduction in a rebuming stage as a function of the NO x concentration entering the rebuming stage, at four different levels of the proportion of heat input supplied by the rebuming stage.
- FIG. 6 is a plot of NO x reduction in a rebuming stage as a function of the proportion of heat input supplied by the rebuming stage, at three different levels of NO x concentration entering the rebuming stage.
- FIG. 7 is a plot of NO x reduction in a rebuming stage as a function of the proportion of heat input supplied by the rebuming stage, at two different residence times in the rebuming stage.
- FIG. 8 is a plot of NO x reduction in a rebuming stage as a function of the proportion of heat input supplied by the rebuming stage, at a NO x concentration of 0.38 lb/MMBtu entering the rebuming stage, for two different rebum fuels, one of which is within the scope of the invention.
- FIG. 9 is a plot of NO x reduction in a rebuming stage as a function of the proportion of heat input supplied by the rebuming stage, at a NO x concentration of 1.0 lb/MMBtu entering the rebuming stage, for two different rebum fuels, one of which is within the scope of the invention.
- FIG. 10 is a plot of NO x emissions from a boiler as a function of heat input to the boiler, comparing a boiler where the primary combustion fuel was straight No. 6 fuel oil with one where the primary combustion fuel was a No. 6 fuel oil emulsion.
- FIG. 11 is a plot of particulate emissions from a boiler as a function of heat input to the boiler, comparing a boiler where the primary combustion fuel was straight No. 6 fuel oil with one where the primary combustion fuel was a No. 6 fuel oil emulsion.
- the residuum-based fuel oils used in this invention are products of the fractional distillation of petroleum at 410 K (390°F) or higher.
- the residuum from the distillation is black and viscous with a boiling temperature in the range of 565°C and higher, and the numbered fuel oils are blends of the residuum and one or more distillate fractions.
- the residuum is termed "vacuum residuum" or “vacuum resid” since it is the residue remaining after the removal of the vacuum gas oil fraction, which is the highest boiling distillate fraction.
- Visbroken residuum also known as "visbreaker pitch” is vacuum residuum that has been heated to reduce its viscosity by thermal cracking. Liquefied coke is achieved by heating coke to a temperature of about 300°F (150°C) or higher, at which temperature coke becomes liquid.
- Nos. 4 and 5 fuel oils are residuum diluted with 20% to 50% distillate, while no. 6 fuel is residuum diluted with 5% to 20% distillate (all by volume).
- the requirements for these fuel oils according to ASTM D 396-92, and their approximate nominal analyses (in weight percents) are as follows:
- aqueous liquid is used herein to denote the continuous phase of the emulsion and consists of water or a homogeneous liquid that is substantially insoluble in the fuel oil and contains water as its major component (i.e., greater than 50% by weight or volume, preferably greater than 90%, and most preferably greater than 95%). Since preferred emulsions of this invention as noted below contain additives, some or all of which are miscible with or soluble in water, the aqueous liquid is preferably an aqueous solution of these additives. 6
- the emulsion is a macroemulsion, which term is used according to its recognized meaning among those skilled in emulsion technology, and denotes an emulsion in which the dispersed phase droplets are of a size that is large enough to provide the emulsion with a milky or cloudy appearance rather than a clear appearance. Otherwise stated, a macroemulsion is one whose dispersed phase droplets are of a size that if the dispersed and continuous phases alone were colorless clear liquids, the emulsion itself would be milky or cloudy. This is distinguishable from a microemulsion, in which the droplets are small enough to give the emulsion the appearance of a homogeneous single liquid phase.
- the macroemulsion of this invention is one in which the dispersed phase is the fuel oil and the continuous phase is the aqueous liquid.
- the droplet size can be controlled to some extent by physical shearing, using conventional shearing pumps or similar mixing equipment.
- the droplet size can also be controlled by the selection and amounts of additives such as surface active agents to stabilize the emulsion.
- the relative amounts of dispersed and continuous phases can vary while still falling within the scope of the invention.
- the dispersed phase will generally constitute from about 50% to about 85% by volume of the macroemulsion, preferably from about 55% to about 80% by volume, more preferably from about 60% to about 75% by volume, and most preferably from about 65% to about 70% by volume. In other embodiments of the invention, the dispersed phase will constitute from about 30% to about 50% by volume of the macroemulsion.
- the emulsion stabilizer can be an emulsifying agent or a mixture of emulsifying agents.
- the choice of emulsifying agent(s) is not critical to this invention; a wide variety of emulsifying agents, including anionic, cationic and nonionic agents, can be used.
- Nonionic emulsifiers are preferred.
- Preferred classes of nonionic emulsifiers are alkyl ethoxylates, ethoxylated alkylphenols and alkyl glucosides.
- nonionic emulsifier is IGEPAL CO-630 (nonylphenoxypoly(ethyleneoxy)ethanol; nonoxynol-8), available from Rhone-Poulenc, Cranbury, New Jersey, USA.
- TERGITOL® NP-9 ⁇ - (4-nonylphenyl)- ⁇ -hydroxypoly(oxy-l,2-ethanediyl), available from Union Carbide Corporation, Danbury, Connecticut, USA.
- amphoteric emulsifiers are any of the various products bearing the trade name MLRATATNE®, which are betaine derivatives, also available from Rhone-Poulenc. Combinations of IGEPAL CO-630 and MLRATATNE are particularly effective in some cases. 7
- the emulsifying agent can be one of a mixture of additives, other components of the mixture being agents that serve a variety of functions, such as for example increasing lubricity, heat stabilization, foam control or prevention, and rust control or prevention.
- Lubricity enhancers are well known, and any of the known variety can be used. Prominent examples are dicarboxylic acids such as DIACID 1525, 1550 and 1575, available from Westvaco Chemical Division, Charleston Heights, South Carolina, USA. Heat stabilizers are similarly well known. Included among these are amphoteric surfactants such as betaine derivatives and tallow glycinate.
- Antifoam agents are likewise well known, examples of which are the sulfates of long- chain alcohols, specific examples of which are the products sold under the trade name RHODAPON (RHODAPON OS, RHODAPON OLS, RHODAPON SB, RHODAPON SM, RHODAPON TDS, RHODAPON UB, and RHODAPON TEA) by Rhone-Poulenc, Inc., Monmouth Junction, New Jersey, USA. Antimst agents are likewise well known.
- Examples are AMP-95 (2-amino-2-methyl-l-propanol, available from Angus Chemical Co., Buffalo Grove, Illinois, USA) and SYNKAD® 828 (borate or carboxylate salts, available from Ferro Corporation, Keil Chemical Division, Hammond, Indiana, USA).
- SYNKAD® 828 borate or carboxylate salts, available from Ferro Corporation, Keil Chemical Division, Hammond, Indiana, USA.
- an additive mixture that contains both AMP-95 and SYNKAD 828 is particularly effective in maintaining a stable emulsion.
- the formation of the emulsion can be facilitated by the incorporation of a mixing aid.
- a mixing aid Any of the wide variety of additives known for their ability to serve as mixing aids can be used.
- Preferred mixing aids in the present invention are alcohols, particularly saturated alkyl alcohols. Prominent among these are C,-C 4 saturated alkyl alcohols, and of these the C C 3 saturated alkyl alcohols are more preferred. Particularly preferred examples are methanol and ethanol.
- the amount of alcohol used is not critical; any amount that will enhance the mixing of the fuel oil and the aqueous liquid can be used. This amount may vary depending on the proportions of the two liquid phases and on the selection and amounts of other additives present.
- an amount of alcohol within the range of from about 0.3% to about 10% by volume of the macroemulsion will provide the best results, preferably from about 0.5% to about 5% by volume, and most preferably from about 1% to about 4% by volume.
- the remaining additives i.e., the emulsifying agent, lubricity additive, heat stabilizer, antifoam agent, and rust inhibitor (whether all or some of these are included) may vary in amounts as well, the effects of varying the amounts being generally known to those skilled in the use of these additives.
- the total of these additives other than the alcohol will range from about 0.05% to about 5% by volume of the macroemulsion, preferably from about 0.1% to about 3% by volume, and most preferably from about 0.1% to about 1% by volume. 8
- the macroemulsion of this invention is prepared by heating No. 6 fuel oil and water (or aqueous liquid) separately, mixing the two liquids thus heated, and shearing the mixture to achieve the droplet dispersion that constitutes the macroemulsion.
- the temperatures to which the two separate phases are heated can vary, generally between about 60°C and about 95°C (140°F-203°F), preferably between about 62°C and about 90°C (144°F-194°F), and more preferably between about 65°C and about 85°C (149°F-185°F), and most preferably between about 67°C and about 75°C (153°F-167°F).
- the temperatures to which the two phases are individually heated prior to mixing will be within about 10°C of each other (18°F), preferably within about 5°C of each other (9°F), and most preferably will be substantially the same.
- the emulsion can be formed by adding the water in the form of superheated steam or pressurized water or steam at a temperature high enough that the residuum is liquid.
- a preferred temperature for the steam or water is about 205 °C (400°F) or higher, preferably from about 205°C to about 300°C.
- a preferred temperature for the steam or water is about 150°C (300°F) or higher, preferably from about 150°C to about 250°C. If pressurized water or steam is used, best results will be obtained with pressures in the range of from about 30 psi to about 150 psi.
- the emulsion stabilizing additives are preferably added before the shearing step.
- the alcohol, when included, is likewise preferably added before the shearing step.
- Shearing is accomplished by conventional means, utilizing any of the various types of mixing and shearing equipment known in the chemical process industry. Examples are fluid foil impellers, axial-flow turbines, flat-blade turbines, jet mixers, and the like.
- the shear pressure may vary, although best results are obtained with a shear pressure within the range of from about 100 psi to about 200 psi, with about 150 psi preferred.
- the macroemulsion fuel of this invention is useful in a wide variety of heat generation units, including boilers and fumaces of various types.
- the macroemulsion can be used in applications where the nonaqueous fuel oil itself is otherwise used, with the macroemulsion serving as a substitute for the fuel oil.
- ways in which the macroemulsion can be used are (1) as a total replacement for the nonaqueous fuel oil in applications in which the fuel oil has heretofore been used, (2) as a fuel in combination with other fuels that are not oils, notably coal, and (3) as a rebumer fuel for boilers and fumaces.
- Rebuming is a means of controlling NO, emissions in boilers and fumaces, and involves injecting a portion of the fuel downstream of the main burners (i.e., the primary combustion zone) to cause further combustion of the primary combustion product in a fuel- rich reducing zone.
- the primary fuel can be any of a variety of fuels, including natural gas, coal, and fuel oils.
- additional air is injected downstream of the injection point of the rebuming fuel.
- the overfire air serves to oxidize any carbon monoxide or other combustibles that are generated in the rebum zone.
- the amount of rebuming fuel injected relative to the fuel fed to the primary combustion zone is conveniently expressed in terms of the heat content of the fuel.
- the heat content itself may be expressed as a percentage of the total heat content of both the rebum fuel and the primary fuel. While the relative amounts are not critical to this invention, the efficiency of the macroemulsion in lowering the NO x concentration of the flue gas will vary with the amount of heat input supplied by the macroemulsion.
- the macroemulsion supplies from about 15% to about 30% of the total heat input to the unit, preferably from about 18% to about 24%, and most preferably about 20%.
- the efficiency of the rebum stage may also vary with the NO x concentration of the combustion product leaving the primary combustion stage, although again this is not critical to this invention.
- the NO x concentration of the combustion product will vary with the type of boiler or furnace and the type of primary fuel used. In general, however, best results in terms of NO x reduction will be obtained with a primary combustion stage product mixture containing from about 100 to about 3,000 ppm by weight of NO x , and preferably from about 250 to about 1,000 ppm by weight of NO x .
- Rebuming can affect the performance of a boiler or furnace in terms of the thermal efficiency of the unit and, in the case of boilers, the steam temperature.
- the water in the macroemulsions of this invention will add to the latent heat loss in the unit.
- the quantity of fuel needed to achieve a given reduction in NO x can be expected to be greater in view of the need to compensate for the increased heat loss.
- the amount of increase required will be readily apparent to those skilled in the art.
- the analysis of the oil was 0.65% water, 85.40% carbon, 10.47% hydrogen, 0.56% nitrogen, 1.53% sulfur, 0.04% ash, and 1.35% oxygen (by difference) (all percents by weight).
- An additive mixture was prepared by combining 14 parts by volume of TERGITOL NP-9 surfactant, 2 parts by volume DIACLD 1525 lubricity additive, and 1 part by volume of REWOTERIC AM TEG heat stabilizer.
- the fuel oil and water were heated separately to about 160°F (71°C), and 67.55 parts by volume of the heated fuel oil were mixed with 30 parts by volume of the heated water. Added to these were 0.45 parts by volume of the additive mixture described in the preceding paragraph, 2 parts by volume of ethanol, and 2 ppm by volume of RHODAPON TEA antifoam. Shearing was performed on a shear pump with 140 psi shear, although higher shears can be used and may be preferable.
- the resulting macroemulsion had a specific gravity (60/60°F, 15/15°C) of 0.9923, a heating value of 105,767 Btu/gal, a kinematic viscosity (40°C) of 18.37 cSt, and a flash point of 185°F (85°C), and was readily pumpable at ambient temperature (20-25°C).
- This example illustrates the use of a No. 6 fuel oil emulsion of this invention as a rebum fuel in a natural gas-fired boiler.
- the tests were performed in a 1.0 MM Btu/h boiler simulation facility that was designed to provide an accurate subscale simulation of the furnace gas temperatures, residence times, and composition of a full scale utility boiler.
- the facility consisted of a burner, a vertically down-fired radiant furnace, a horizontal convective pass, and a baghouse.
- a variable swirl diffusion burner with an axial fuel injector was used to simulate the temperature and gas composition of a commercial burner in a full scale boiler. Primary air was injected axially, while the secondary air stream was injected radially through the swirl vanes to provide controlled fuel/air mixing. The swirl number was controlled by adjusting the swirl vanes.
- the cylindrical furnace section of the facility was constructed of eight modular refractory-lined sections with an inside diameter of 22 inches.
- the convective pass was also refractory lined, and contained air-cooled tube bundles to simulate the superheater and reheater sections of a full scale utility boiler.
- the flame in the facility was typically 3-4 feet long.
- the rebum fuel was injected just downstream of the flame to establish a reducing zone.
- Overfire air was injected in the lower part of the furnace at 2,300°F (1,260°C) to oxidize CO and any residual combustibles generated in the rebum zone.
- Residence time in the rebum zone was 0.5 second except where otherwise noted.
- the initial NO x concentration was controlled by metering gaseous ammonia into the primary combustion air. This provided close control over furnace NO x levels.
- Stoichiometric ratios of air to fuel were set at three locations — the primary bum zone (i.e., the air/fuel mixture fed to the main burners), the secondary bum zone (the rebum zone immediately after injection of the rebum fuel), and the final bum zone (after injection of the overfire air).
- the term "SRI" is used to indicate the stoichiometric ratio in the primary bum zone, "SR2" the ratio in the secondary bum zone, and "SRf ' the ratio in the final bum zone. The value of SRI used in the tests was 1.10 and the value of SRf was 1.15.
- the total firing rate in all tests in this series was 840,000 Btu/h.
- Natural gas was used as the main fuel for all tests in this example.
- the fuels used for rebuming included natural gas, a naphtha water emulsion with 30% water, and two No. 6 fuel oil emulsions, one containing 30% water and the other containing 40% water (all by volume).
- Each emulsion was stabilized by an additive mixture formed by combining 15 liters of NONYLPHENOL 9MOL surfactant (nonylphenol +9 EO polyethoxylate), 2 liters of REWOTERIC AM TEG (dihydroxyethyl tallow glycinate), 2 liters of DIACID 1550 (a C 21 dicarboxylic acid), 2 liters of AMP 95 (2-amino-2-methyl-l-propanol), 4 liters of SYNKAD 828 (a carboxylic acid salt), 1-3/4 oz. of RHODAPON TEA (triethanolamine lauryl sulfate), and 10 liters of methanol.
- the proportion of additive mixture to the total emulsion was approximately 0.9% by volume.
- Table II summarizes analyses for the naphtha and No. 6 oil emulsions with 30% water.
- Heating Value (Btu lb 13,709 12,849 as fired) It was determined that all emulsions, including those made with No. 6 oil, could be pumped and atomized without the need to preheat above the ambient temperature of approximately 65°F (18°C).
- the emulsions were pumped using a progressive cavity pump and atomized using a twin-fluid atomizer with nitrogen as the atomization medium.
- the rebum injector was elbow-shaped and was installed along the centerline of the furnace, countercurrent to the gas flow.
- FIG. 1 shows a performance comparison of the different reburn fuels (natural gas represented by squares, naphtha emulsion by diamonds, and No. 6 fuel oil emulsion with 30% water by circles) as a function of rebum heat input (expressed as a percentage of the total heat input into the boiler) at an initial NO x concentration of 450 ppm.
- NO x control progressively increased as rebum heat input was increased from 10 to 20%, and then levelled off as rebum heat input was further increased to 24%.
- Natural gas provided the highest NO x control, followed by the naphtha emulsion and the No. 6 oil emulsion with 30% water.
- initial NO x 450 ppm
- the highest NO x control provided by natural gas was 70%, as compared to 59% by No. 6 oil emulsion. 13
- FIG. 2 compares rebum performance of natural gas (represented by squares), the naphtha emulsion (circles), and the No. 6 fuel oil emulsion (triangles) at an initial NO x concentration of 800 ppm.
- rebum heat inputs 20% or higher, similar NO x reductions were obtained with each rebum fuel.
- each of the three rebum fuels provided between 72 and 73% NO x control.
- FIG. 3 presents the same comparison as a function of rebum zone stoichiometry (natural gas represented by squares, naphtha emulsion by circles, and No. 6 fuel oil emulsion by triangles).
- SR2 values below 0.9 NO x reductions were approximately insensitive to SR2 and were similar for each test fuel.
- FIG. 4 presents a rebum performance comparison between the No. 6 fuel oil emulsion containing 30% water (filled circles and triangles) and the No. 6 fuel oil emulsion containing 40% water (open circles and triangles), each at initial NO x concentrations of 300 ppm (circles) and 800 ppm (triangles). At each initial NO x concentration, NO x reduction was higher by 1 to 4 percentage points for the emulsion with 30% water as compared to the emulsion with 40% water.
- the NO x concentration in the combustion gas produced by the main burners in a boiler can vary with composition of the fuel to the burners, the boiler design, the flame zone temperature, and the type of burner used.
- the effectiveness of rebuming generally decreases as initial NO x concentration decreases; this is due to kinetic limitations in the rebuming reactions. For this reason, rebum tests using emulsions in accordance with the present invention were conducted at initial NO concentrations of 300, 450, and 800 ppm.
- FIG. 5 shows the performance of the fuel oil No. 6 emulsion (with 30% water) as a function of initial NO x concentration.
- Tests with 10% rebuming are represented by circles; tests with 15% rebuming are represented by squares; tests with 20% rebuming are represented by diamonds; and tests with 24% rebuming are represented by diamonds.
- NO x reduction increases significantly with increasing initial NO concentration. At 20% rebuming, NO reduction increased from 50% when the initial NO x concentration was 300 ppm to 70% when the initial NO concentration was 800 ppm.
- FIG. 6 presents this data as a function of rebum heat input (expressed as percentage of the total heat input) for the three different initial NO x concentrations — 300 ppm represented by circles; 450 ppm represented by triangles; and 800 ppm represented by squares.
- the performance curve is much steeper at the initial NO x concentration of 800 ppm than at initial NO concentration of 300 ppm.
- the performance difference between initial NO x concentration values of 300 and 800 ppm is only 8 percentage points, while at 24% rebuming the difference is 22 percentage points. This indicates that No. 6 oil emulsion rebuming is particularly effective in boilers with high initial NO x concentrations.
- overfire air To cause rebuming to occur, overfire air must be injected in the rebum zone either upstream of the banks of convective tubes or in between the banks.
- the location of the overfire air injectors determines the residence time in the rebum zone, and in full scale boilers, the location of these injectors is subject to spatial limitations in the boiler design. Reburn NO x control generally increases with increasing rebum zone residence time.
- the NO x reduction increases with increasing residence time, and the impact of residence time on NO x reduction increases with increasing rebum heat input.
- NO x reduction was 65% at 0.75 sec residence time, as compared to 58% at 0.50 sec.
- This example illustrates the use of a No. 6 fuel oil emulsion of this invention as a rebum fuel in a pulverized coal- fired boiler (i.e., a boiler using pulverized coal as its main fuel), and in a cyclone fired boiler.
- the pulverized coal-fired boiler was simulated by a boiler whose main fuel was natural gas but whose initial NO x concentration was 0.38 lbm/MMBtu.
- NO x emissions decreased from 0.38 lb/MMBtu with no rebuming to 0.18 lb/MMBtu at 20% rebuming, as shown in FIG. 8 (circles).
- FIG. 8 also shows the results obtained with natural gas as the rebum fuel (squares).
- the cyclone fired boiler was simulated a boiler whose main fuel was natural gas but whose initial NO concentration was 1.0 lbm MMBtu.
- NO x emissions decreased from 1.0 lb/MMBtu with no 15 rebuming to 0.27 lb/MMBtu at 24% rebuming, as shown in FIG. 9 (circles).
- FIG. 8 also shows the results obtained with natural gas as the rebum fuel (squares).
- This example illustrates the use of a No. 6 fuel oil emulsion of this invention as the primary combustion fuel in a boiler, comparing these results to those obtained using No. 6 fuel oil itself (in the absence of water and not emulsified).
- the boiler was a three-pass firetube "Scotch" marine-type boiler whose burner was rated at 2.5 x 10 6 Btu/h with a ring-type natural gas burner and an air-atomizing center nozzle oil burner.
- the boiler had 300 square feet of heating surface and was capable of generating up to 2,400 lb/h saturated steam at pressures up to 15 psig.
- the boiler was equipped with instrumentation for continuous emission monitoring for various emissions including NO x , using a Rosemount Analytical Model 951 A NO x analyzer operating by chemiluminescence and accurate to 0.5% of full scale. Particulate matter in the flue gas was measured in a sampling train by conventional techniques, with three samples taken per test condition.
- the No. 6 fuel oil and No. 6 fuel oil emulsion used were those described in Example 2 above, the emulsion containing 30% water.
- the test results included a comparison of NO x emissions as a function of heat input to the boiler, for both straight No. 6 fuel oil and the No. 6 fuel oil emulsion. These results are plotted in FIG.
- the NO x emissions were reduced by amounts within the range of 24% to 40% by replacing the straight No. 6 fuel oil (filled circles) with the emulsion (x's).
- the NO x emissions were 0.237 lb/MMBtu at a heat input of 1.60 MMBtu/h, and 0.220 lb/MMBtu at a heat input of 2.07 MMBtu h.
- the NO x emissions were 0.142 lb/MMBtu at a heat input of 1.88 MMBtu h, and 0.143 lb/MMBtu at a heat input of 1.93 MMBtu h.
- the particulate matter emissions are plotted in FIG. 11 as a function of heat input to the boiler. These results likewise show a substantial reduction due to the replacement of the straight No. 6 fuel oil (filled circles) with the emulsion (x's).
- the straight fuel oil the particulate emissions rose from 0.035 lb/MMBtu at a heat input of 1.61 MMBtu/h to 0.041 lb/MMBtu at a heat input of 2.06 MMBtu/h
- the particulate emissions rose from 0.032 lb/MMBtu at a heat input of 1.88 MMBtu h to 0.035 lb/MMBtu at a heat input of 1.93 MMBtu/h.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU36514/99A AU738853B2 (en) | 1998-04-22 | 1999-04-22 | Aqueous emulsion fuels from petroleum residuum-based fuel oils |
JP55318999A JP2001508831A (en) | 1998-04-22 | 1999-04-22 | Aqueous emulsion fuel derived from petroleum residue-based fuel oil |
EP99918651A EP1000129A1 (en) | 1998-04-22 | 1999-04-22 | Aqueous emulsion fuels from petroleum residuum-based fuel oils |
CA002293249A CA2293249A1 (en) | 1998-04-22 | 1999-04-22 | Aqueous emulsion fuels from petroleum residuum-based fuel oils |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6467898A | 1998-04-22 | 1998-04-22 | |
US09/064,678 | 1998-04-22 | ||
US09/081,867 US6187063B1 (en) | 1998-04-22 | 1998-05-20 | Aqueous emulsion fuels from petroleum residuum-based fuel oils |
US09/081,867 | 1998-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999054426A1 true WO1999054426A1 (en) | 1999-10-28 |
Family
ID=26744779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/008492 WO1999054426A1 (en) | 1998-04-22 | 1999-04-22 | Aqueous emulsion fuels from petroleum residuum-based fuel oils |
Country Status (8)
Country | Link |
---|---|
US (1) | US6187063B1 (en) |
EP (1) | EP1000129A1 (en) |
JP (1) | JP2001508831A (en) |
KR (1) | KR100456334B1 (en) |
CN (1) | CN1255518C (en) |
AU (1) | AU738853B2 (en) |
CA (1) | CA2293249A1 (en) |
WO (1) | WO1999054426A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6840290B2 (en) | 2000-12-06 | 2005-01-11 | Bp Oil International Limited | Process and apparatus for fuelling a marine vessel |
WO2005021691A3 (en) * | 2003-08-22 | 2005-04-21 | Lubrizol Corp | Emulsified fuels and engine oil synergy |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7279017B2 (en) * | 2001-04-27 | 2007-10-09 | Colt Engineering Corporation | Method for converting heavy oil residuum to a useful fuel |
US7344570B2 (en) | 2001-08-24 | 2008-03-18 | Clean Fuels Technology, Inc. | Method for manufacturing an emulsified fuel |
WO2003033626A2 (en) * | 2001-10-16 | 2003-04-24 | Ralph Wong | Fuel mixture for compression ignition device |
CA2404586C (en) * | 2002-09-23 | 2010-10-05 | Imperial Oil Resources Limited | Integrated process for bitumen recovery, separation and emulsification for steam generation |
US20040111957A1 (en) * | 2002-12-13 | 2004-06-17 | Filippini Brian B. | Water blended fuel composition |
WO2005044958A2 (en) * | 2003-10-28 | 2005-05-19 | Technol Fuel Conditioners, Inc. | Heavy oil emulsion stabilizers containing saccharide based emulsion stabilizer |
US7341102B2 (en) * | 2005-04-28 | 2008-03-11 | Diamond Qc Technologies Inc. | Flue gas injection for heavy oil recovery |
US20110265370A1 (en) * | 2005-11-14 | 2011-11-03 | German Avila | Three phase emulsified fuel and method of preparation and use |
DE602007011124D1 (en) * | 2006-02-07 | 2011-01-27 | Colt Engineering Corp | Carbon dioxide enriched flue gas injection for hydrocarbon recovery |
US7828861B1 (en) | 2006-12-12 | 2010-11-09 | Ralph Wong | Method of forming fuel mixture for compression ignition device |
EP1935969A1 (en) * | 2006-12-18 | 2008-06-25 | Diamond QC Technologies Inc. | Multiple polydispersed fuel emulsion |
US20080148626A1 (en) * | 2006-12-20 | 2008-06-26 | Diamond Qc Technologies Inc. | Multiple polydispersed fuel emulsion |
JP4472013B2 (en) * | 2009-01-30 | 2010-06-02 | 進 稲澤 | Water-in-oil emulsion fuel |
KR101357772B1 (en) * | 2012-10-15 | 2014-02-03 | 김철호 | Manufacturing method for alternative emulsification fuel oil instead of b-c oil using petroleum cokes |
CN109529770B (en) * | 2018-12-29 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Method for preparing porous carbon adsorbent material by taking semicoke-stable Pickering emulsion as template |
CN115477965A (en) * | 2022-09-27 | 2022-12-16 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Heavy fuel oil and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3958915A (en) * | 1974-02-15 | 1976-05-25 | The Toyo Rubber Industry Co., Ltd. | Method of burning emulsion oils |
US4877414A (en) * | 1988-03-31 | 1989-10-31 | Kenneth Mekonen | Fuel compositions |
US4943390A (en) * | 1983-11-02 | 1990-07-24 | Petroleum Fermentations N.V. | Bioemulsifier-stabilized hydrocarbosols |
US5078064A (en) * | 1990-12-07 | 1992-01-07 | Consolidated Natural Gas Service Company, Inc. | Apparatus and method of lowering NOx emissions using diffusion processes |
US5503772A (en) * | 1991-12-02 | 1996-04-02 | Intevep, S.A. | Bimodal emulsion and its method of preparation |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3006142A (en) * | 1959-12-21 | 1961-10-31 | Phillips Petroleum Co | Jet engine combustion processes |
US4400177A (en) * | 1979-09-24 | 1983-08-23 | Cottell Eric Charles | Fuels and methods for their production |
DE3525124A1 (en) * | 1985-07-13 | 1987-01-15 | Huels Chemische Werke Ag | FUELS AND HEATING OILS AND USE OF AN EMULGATOR SYSTEM FOR THE PRODUCTION OF THESE FUELS AND HEATING OILS |
US5283001A (en) * | 1986-11-24 | 1994-02-01 | Canadian Occidental Petroleum Ltd. | Process for preparing a water continuous emulsion from heavy crude fraction |
US5156652A (en) * | 1986-12-05 | 1992-10-20 | Canadian Occidental Petroleum Ltd. | Low-temperature pipeline emulsion transportation enhancement |
GB8717836D0 (en) * | 1987-07-28 | 1987-09-03 | British Petroleum Co Plc | Preparation & combustion of fuel oil emulsions |
CA2000964A1 (en) * | 1989-03-02 | 1990-09-02 | Richard W. Jahnke | Oil-water emulsions |
US5354504A (en) * | 1991-08-19 | 1994-10-11 | Intevep, S.A. | Method of preparation of emulsions of viscous hydrocarbon in water which inhibits aging |
US5284492A (en) * | 1991-10-01 | 1994-02-08 | Nalco Fuel Tech | Enhanced lubricity fuel oil emulsions |
US5743922A (en) * | 1992-07-22 | 1998-04-28 | Nalco Fuel Tech | Enhanced lubricity diesel fuel emulsions for reduction of nitrogen oxides |
JPH06322382A (en) * | 1993-03-17 | 1994-11-22 | Kao Corp | Residual oil emulsion fuel composition |
-
1998
- 1998-05-20 US US09/081,867 patent/US6187063B1/en not_active Expired - Lifetime
-
1999
- 1999-04-22 JP JP55318999A patent/JP2001508831A/en active Pending
- 1999-04-22 CN CNB998007765A patent/CN1255518C/en not_active Expired - Fee Related
- 1999-04-22 AU AU36514/99A patent/AU738853B2/en not_active Ceased
- 1999-04-22 WO PCT/US1999/008492 patent/WO1999054426A1/en not_active Application Discontinuation
- 1999-04-22 KR KR10-1999-7012130A patent/KR100456334B1/en not_active IP Right Cessation
- 1999-04-22 CA CA002293249A patent/CA2293249A1/en not_active Abandoned
- 1999-04-22 EP EP99918651A patent/EP1000129A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3958915A (en) * | 1974-02-15 | 1976-05-25 | The Toyo Rubber Industry Co., Ltd. | Method of burning emulsion oils |
US4943390A (en) * | 1983-11-02 | 1990-07-24 | Petroleum Fermentations N.V. | Bioemulsifier-stabilized hydrocarbosols |
US4877414A (en) * | 1988-03-31 | 1989-10-31 | Kenneth Mekonen | Fuel compositions |
US5078064A (en) * | 1990-12-07 | 1992-01-07 | Consolidated Natural Gas Service Company, Inc. | Apparatus and method of lowering NOx emissions using diffusion processes |
US5078064B1 (en) * | 1990-12-07 | 1999-05-18 | Gas Res Inst | Apparatus and method of lowering no emissions using diffusion processes |
US5503772A (en) * | 1991-12-02 | 1996-04-02 | Intevep, S.A. | Bimodal emulsion and its method of preparation |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6840290B2 (en) | 2000-12-06 | 2005-01-11 | Bp Oil International Limited | Process and apparatus for fuelling a marine vessel |
WO2005021691A3 (en) * | 2003-08-22 | 2005-04-21 | Lubrizol Corp | Emulsified fuels and engine oil synergy |
Also Published As
Publication number | Publication date |
---|---|
KR20010020478A (en) | 2001-03-15 |
CN1255518C (en) | 2006-05-10 |
US6187063B1 (en) | 2001-02-13 |
JP2001508831A (en) | 2001-07-03 |
CA2293249A1 (en) | 1999-10-28 |
AU738853B2 (en) | 2001-09-27 |
AU3651499A (en) | 1999-11-08 |
KR100456334B1 (en) | 2004-11-09 |
EP1000129A1 (en) | 2000-05-17 |
CN1272131A (en) | 2000-11-01 |
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